EP0321407A2 - Flexibilised epoxy resin compositions - Google Patents

Flexibilised epoxy resin compositions Download PDF

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Publication number
EP0321407A2
EP0321407A2 EP88810851A EP88810851A EP0321407A2 EP 0321407 A2 EP0321407 A2 EP 0321407A2 EP 88810851 A EP88810851 A EP 88810851A EP 88810851 A EP88810851 A EP 88810851A EP 0321407 A2 EP0321407 A2 EP 0321407A2
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EP
European Patent Office
Prior art keywords
aliphatic
anion
compositions according
mixture
acid
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EP88810851A
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German (de)
French (fr)
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EP0321407A3 (en
EP0321407B1 (en
Inventor
Aloysius Hubertus Manser
Dieter Dr. Strasilla
Rolf Dr. Mülhaupt
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Novartis AG
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Ciba Geigy AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to new epoxy resin compositions, the cured products and the use of the epoxy resin compositions as adhesives or as coating agents.
  • Hardened epoxy resins are generally brittle materials that have low peel and impact strengths. In order to counteract this embrittlement, flexibilizers are added to the epoxy resin. Examples of this are elastic prepolymers, such as adducts of epoxy resins with carboxyl- or amino-terminated butadiene / acrylonitrile copolymers or carboxyl-terminated polyesters. These additives can degrade other desirable properties, such as lowering the tensile shear strength of the cured formulation. Mixtures of epoxy resins and metallocene complex salts are known from EP-A-94,915. The mixtures can be activated by irradiation and cured in a thermal step.
  • All epoxy resins with an average of at least two 1,2-epoxy groups in the molecule are generally suitable as component A). These connections include, for example:
  • Polyglycidyl and poly ( ⁇ -methylglycidyl) esters obtainable by reacting a compound having at least two carboxyl groups in the molecule and epichlorohydrin or glycerol dichlorohydrin or ⁇ -methylepichlorohydrin. The reaction is conveniently carried out in the presence of bases.
  • Aliphatic, cycloaliphatic or aromatic polycarboxylic acids can be used as the compound having at least two carboxyl groups in the molecule. Examples of these polycarboxylic acids are listed below as forming components of the polyester C).
  • Polyglycidyl or poly ( ⁇ -methylglycidyl) ether obtainable by reacting a compound with at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.
  • Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol or poly-oxypropylene) glycols, propane-1,3-diol, butane 1,4-diol, poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerin, 1,1,1-trimethylolpropane, pentaerythritol, Sorbitol and polyepichlorohydrins.
  • acyclic alcohols such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol or poly-oxypropylene) glycols, propane-1,3-diol, butane 1,4-diol, poly (
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1 , 1-bis (hydroxymethyl) cyclohex-3-ene.
  • the epoxy compounds can also be derived from mononuclear phenols, such as resorcinol or hydroquinone; or they are based on polynuclear phenols such as, for example, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and on novolaks obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde , Chloral or furfuraldehyde with phenols such as phenol, or with phenols which are substituted in the core with chlorine atoms or C 1 -C 6 -alkyl groups, such as 4-chlorophenol, 2-methylphenol or 4-tert-butylphe nol or
  • Poly (S-glycidyl) compounds in particular di-S-glycidyl derivatives, which are derived from dithiols, such as, for example, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.
  • Cycloaliphatic epoxy resins such as bis (2,3-epoxicyclopentyl) ether, 2,3-epoxicyclopentylglycidyl ether or 1,2-bis (2,3-epoxycyclopentyloxy) ethane or 3,4-epoxicyclohexylmethyl-3 ', 4 '-epoxicyclohexane carboxylate.
  • epoxy resins can also be used in which the 1,2-epoxy groups are bonded to different heteroatoms or functional groups; These compounds include, for example, the glycidyl ether glycidyl ester of salicylic acid.
  • a mixture of epoxy resins can be used in the mixtures according to the invention.
  • epoxy resins are known per se or can be produced by known processes.
  • component B) come as ⁇ -arenes R 1 and R 2 in particular carbocyclic-aromatic hydrocarbons with 6 to 24 carbon atoms, in particular with 6 to 12 carbon atoms, or heterocyclic-aromatic hydrocarbons with 4 to 11 carbon atoms and one or two S and / or O-atoms are suitable, these groups being mono- easy optionally substituted by identical or different monovalent radicals, such as halogen atoms, preferably chlorine or bromine atoms or Ci-C 8 alkyl, C 1 -C 8 alkoxy, or phenyl or polysubstituted, preferably or can be substituted twice.
  • halogen atoms preferably chlorine or bromine atoms or Ci-C 8 alkyl, C 1 -C 8 alkoxy, or phenyl or polysubstituted, preferably or can be substituted twice.
  • R 2 can also be an indenyl anion and in particular a cyclopentadienyl anion, it also being possible for these anions to be mono- or polysubstituted, preferably mono- or disubstituted, by the same or different monovalent radicals, as mentioned above as substituents for n-arenes.
  • alkyl or alkoxy substituents can be straight-chain or branched.
  • Typical alkyl or alkoxy substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and n-octyl, methoxy, ethoxy, n-propoxy , Called isopropoxy, n-butoxy, n-hexyloxy and n-octyloxy.
  • Alkyl and alkoxy groups with 1 to 4 and in particular 1 or 2 carbon atoms in the alkyl parts are preferred.
  • Preferred substituted ⁇ -arenes or substituted indenyl or cyclopentadienyl anions are those which contain one or two of the above-mentioned substituents, in particular methyl, ethyl, n-propyl, isopropyl, methoxy or ethoxy groups.
  • n-arenes can be present as R i and R 2 .
  • n-arenes examples include benzene, toluene, xylenes, ethylbenzene, cumene, methoxybenzene, ethoxybenzene, dimethoxybenzene, p-chlorotoluene, m-chlorotoluene, chlorobenzene, bromobenzene, dichlorobenzene, trimethylbenzene, trimethoxybenzene, dihydro-naphthalene, naphthalene, 1,2-naphthalene, naphthalene , 2,3,4-tetrahydronaphthalene, methylnaphthalene, methoxynaphthalene, ethoxynaphthalene, chloronaphthalene, bromnaphthalene, biphenyl, stilbene, indene, 4,4'-dimethylbiphenyl, fluorene, phenanthrene, anthracene, 9,10-d
  • anions of substituted cyclopentadienes are the anions of methyl, ethyl, n-propyl and n-butylcyclopentadiene or the anions of dimethylcyclopentadiene.
  • Preferred anions are the anion of the unsubstituted indene and in particular the unsubstituted cyclopentadiene.
  • the index a is preferably 1.
  • the index b is preferably 1.
  • R 2 is preferably each the optionally substituted indenyl anion or in particular the cyclopentadienyl anion.
  • X ° prefers the anion of a perfluoroaliphatic or perfluoroaromatic sulfonic acid and very particularly [LQ m] °, as defined above.
  • Examples of anions of perfluoroaliphatic or perfluoroaromatic sulfonic acids are CF 3 SO , C 2 F 5 SO , nC 3 F 7 SO , nC 4 F 9 SO , nC 6 F 13 SO , nC 8 F 17 SO , C 6 F 5 SO and CF 3 C 6 F 4 SO .
  • Examples of particularly preferred anions [LQ m] ° are PF °, AsF , SbF and SbF 5 (OH) ⁇ . AsF are particularly preferred , SbF9 and SbF 5 (OH) ⁇ and in particular SbF .
  • Curable mixtures containing initiators with these very particularly preferred anions can be cured at low temperatures after their activation by irradiation.
  • the compounds of formula 1 are known per se or can be prepared analogously to known compounds.
  • Compounds of the formula I with other anions can be produced in deviation from the processes described therein by introducing another anion of the acid HX in a manner known per se instead of an anion of a complex acid; X has the meaning defined above.
  • Component C) can be solid or liquid at room temperature. As a rule, they are linear polyesters or compounds with such a degree of branching or crosslinking that they can be dissolved in an organic solvent without gel residue. The degree of branching or crosslinking can be regulated in a manner known per se by the functionality and amount of polyfunctional condensation components (polyols or polycarboxylic acids).
  • the flexible polyesters C) can be amorphous or partially crystalline and are preferably compatible with the resin component A) or easily dispersible therein.
  • the softening point of the polyester C) is preferably below 100 ° C.
  • the polyesters C) generally have molecular weights (number average) from 250 to 15000, preferably from 500 to 2500.
  • Their acid number is generally 0.1 to 5 equivalents / kg, preferably 0.25 to 2.0 equivalents / kg.
  • the viscosity (according to Epprecht) of these polyesters is generally less than 2000 mPas (at 80 ° C).
  • the carboxyl-terminated flexible polyesters are derived from aliphatic or cycloaliphatic polyols and aliphatic, cycloaliphatic or aromatic polycarboxylic acids.
  • the preferred polyol is hexanediol, which is optionally combined with neopentyl glycol or cyclohexanedimethanol in order to increase the resistance to hydrolysis.
  • Preferred polycarboxylic acids are ⁇ , ⁇ -dicarboxylic acid with aliphatic segments such as e.g. Adipic or sebacic acid.
  • Prepolymer components are generally understood to mean hydroxyl-terminated prepolymers with at least two recurring flexibilizing structural components. Examples of these are hydroxyl-terminated polyethers based on polypropylene and polybutylene glycol and hydroxyl-terminated polycaprolactones. The number average molecular weight of these prepolymers is generally 150-4000, preferably 500-2500.
  • Prepolymeric structural components can be di- or higher-functional, preferably di- or tri-functional. Low molecular weight components are usually difunctional. However, polyester C) can contain small amounts of low-molecular, higher-functional structural components.
  • aliphatic dicarboxylic acids are saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, a-methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid or dimerized linoleic acid; or unsaturated aliphatic polycarboxylic acids, such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, glutaconic acid or itaconic acid, and possible anhydrides of these acids.
  • saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, a-methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid or dimerized linoleic acid
  • unsaturated aliphatic polycarboxylic acids such as maleic acid, fumaric acid,
  • cycloaliphatic dicarboxylic acids are hexahydrophthalic, isophthalic or terephthalic acid, tetrahydrophthalic, isophthalic or terephthalic acid or 4-methyltetrahydrophthalic acid, 4-methylhexahydrophthalic acid or endomethylene tetrahydrophthalic acid.
  • aromatic dicarboxylic acids examples include phthalic, isophthalic and terephthalic acid.
  • higher functional carboxylic acids are aromatic tricarboxylic or tetracarboxylic acids, such as trimellitic acid, trimesic acid, pyromellitic acid or benzophenonetetracarboxylic acid; or trimerized fatty acids or mixtures of dimerized and trimerized fatty acids, as are commercially available, for example, under the name Pripo1 0 .
  • low molecular weight aliphatic diols are ⁇ , ⁇ -alkylene diols, such as ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, neopentyl glycol, hexane -1,6-diol, octane-1,8-diol, decane-3,10-diol or dodecane-1,12-diol.
  • ⁇ , ⁇ -alkylene diols such as ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, neopentyl glycol, hexane -1,6-diol, octane-1,8-diol, decane-3
  • low molecular weight cycloaliphatic diols are 1,3- or 1,4-dihydroxycyclohexane, 1,4-cyclohexane dimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane.
  • low molecular weight higher functional alcohols examples include 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerin or pentaerythritol.
  • Suitable hydroxyl-terminated prepolymers with at least two recurring flexibilizing structural units are polyethers, polyesters or polythioethers, provided that these compounds are hydroxyl-terminated.
  • hydroxyl-terminated polyethers are polyalkylene ether polyols which are produced by ionic polymerization.
  • Copolymerization or block copolymerization of alkylene oxides such as ethylene oxide, propylene oxide or butylene oxide, optionally in the presence of di- or polyfunctional alcohols, such as butane-1,4-diol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, hexane 1,2,6-triol, glycerol, pentaerithritol or sorbitol, or of amines, such as methylamine, ethylenediamine or hexane-1,6-diamine, or by ionic polymerization or copolymerization of cyclic ethers, such as tetrahydrofuran, ethylene oxide or propylene oxide with acidic catalysts, such as BF a ⁇ etherate or by polycondensation of glycols which are
  • polyester polyols examples include compounds which are derived from di- and / or polycarboxylic acids and di- and / or polyols, preferably from dicarboxylic acids and diols.
  • suitable polyols and polycarboxylic acids are listed above as structural components for the polyesters C).
  • suitable hydroxyl-terminated prepolymers are polymerization products of lactones, for example of s-caprolactones; or polyalkylene thioether polyols, for example the polycondensation products of thiodiglycol with and with diols and / or polyols, such as, for example, hexane-1,6-diol, triethylene glycol, 2,2-dimethyl-1,3-propanediol or 1,1,1-trimethylolpropane.
  • the polyester C) is prepared in a manner known per se by reacting the polyol component (s) with an excess of polycarboxylic acid component (s).
  • polycarboxylic acid you can also use a polyester-forming derivative, for example an anhydride.
  • polyol and polycarboxylic acid are condensed, the polyol being used in excess.
  • the resulting prepolymer with hydroxyl groups is then capped with carboxylic acid anhydrides to give the carboxyl-terminated polyester.
  • the polyester resins can be made by general procedures used in the manufacture of such resins.
  • the esterification can conveniently be carried out by melt condensation of the carboxylic acid component (s) and the diol.
  • the reactants are heated, for example, to temperatures up to 250 ° C. with stirring. It may be advisable to pass an inert gas, such as nitrogen, through the reaction mixture in order to remove the water formed during the esterification reaction.
  • an inert gas such as nitrogen
  • a slight vacuum can optionally also be applied in order to isolate residual low-molecular cleavage products.
  • the preferred temperature range for the melt condensation is 160-250 ° C.
  • other forms of polycondensation can also be used, for example interfacial polycondensation, polycondensation in solution, in suspension or in bulk.
  • the polyester C) can be a carboxyl-terminated prepolymer or this adduct is present in a mixture with unreacted carboxylic acid or anhydride.
  • Preferred components A) are polyglycidyl ethers based on phenols and very particularly the diglycidyl ethers of bisphenols.
  • These resins can be liquid or solid.
  • Combinations of liquid bisphenol-based diglycidyl ethers with solid bisphenol-based diglycidyl ethers or with solid polyglycidyl ethers based on phenol-formaldehyde novolaks or cresol-formaldehyde novolaks are preferably used for adhesives.
  • the combinations of liquid and solid bisphenol A diglycidyl ethers are particularly preferred.
  • Preferred components B) are compounds of the formula 1, as defined above, in which R 1 is a mono- or di-alkyl or alkoxy-substituted benzene or naphthalene radical, R 2 is a cyclopentadienyl anion and X ⁇ SbF means.
  • Preferred substituents of the benzene or naphthalene radical are Ci-Cs-alkyl or alkoxy radicals, in particular methyl, ethyl, n-propyl or isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy.
  • Preferred components C) are compounds of the formula II wherein R 3 is a residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after removal of the carboxyl groups, preferably a residue of an aliphatic dicarboxylic acid, in particular a residue of fumaric acid or maleic acid, R 4 is a residue of a dihydric aliphatic or cycloaliphatic alcohol after removal of the hydroxyl groups and c is an integer from 1 to 50.
  • the index c is preferably 2 to 25.
  • Particularly preferred components C) are compounds of the formula 11 in which at least some of the R 4 radicals are divalent radicals of a polyalkylene ether.
  • R 4 include the groups of the formulas lilac, Illb and in particular IIIc where r is an integer from 4 to 25.
  • the curable compositions can also contain other known and customary additives D) used in the art of photopolymerizable materials or adhesives.
  • additives are pigments, dyes, fillers and reinforcing agents, glass fibers and other fibers, flame retardants, antistatic agents, leveling agents, antioxidants, adhesion promoters, plasticizers, wetting agents, thixotropic agents and light stabilizers.
  • compositions according to the invention can also contain combinations of initiators of the formula I and sensitizers.
  • initiators of the formula I in which R 1 is an optionally substituted benzene derivative, an increase in photosensitivity is generally observed when sensitizers are added.
  • suitable sensitizers can be found in EP-A-152,377.
  • Combinations of initiators of the formula I, oxidizing agents and, if appropriate, sensitizers for the compounds I can also be used in the compositions according to the invention. Oxidizing agents usually lower the curing temperatures and allow processing under mild conditions. Suitable oxidizing agents are mentioned in EP-A-126,712.
  • the amount of component A) is generally 40-95% by weight, in particular 50-90% by weight.
  • the Initiator B) is generally present in amounts of 0.1-10% by weight, in particular 0.1 to 5% by weight.
  • the proportion of component C) is generally 5 to 50% by weight, particularly 5 to 30% by weight, and very particularly preferably 10 to 30% by weight, while the proportion of additives D) makes up 0 to 50% by weight can.
  • the curable compositions according to the invention are sensitive to light. They can be obtained in any form, e.g. as homogeneous liquid or solid mixtures.
  • Solid products can be prepared in a manner known per se, for example by liquefying solid epoxy resins, if appropriate with the addition of suitable solvents in the dark or under red light, heating to temperatures above their glass transition point, addition of initiator B) and component C), homogenization and cooling of the resulting mixtures be preserved. If desired, the products thus obtained can then be comminuted.
  • the composition according to the invention can be obtained by simply mixing the components.
  • the curable compositions of the invention are at room temperature in relatively dark, e.g. in red light, storable for considerable time. Depending on their composition and their end purpose, e.g. for the production of coatings or films, they can be thermally hardened directly or in two stages by a combination of radiation and heating.
  • the curing temperature is generally 40-200 ° C., preferably 80-150 ° C., particularly preferably 80-110 ° C.
  • Two-stage polymerization is particularly preferred by first activating the initiator of the formula by irradiating the curable mixture and then thermally curing the activated precursors thus obtained, the irradiation temperature being below that used for subsequent hot curing.
  • These activated precursors can normally be cured at temperatures which are considerably lower than would be required in the absence of component C), preferably at temperatures between 80 and 110 ° C.
  • This two-stage curing also makes it possible to control the polymerization in a particularly simple and advantageous manner.
  • the activated precursors obtainable from the curable compositions according to the invention can generally be stored for a considerable time even at room temperature, in particular in the case of mixtures which contain, as component A), a highly viscous or solid epoxy resin. This feature represents another significant advantage of the two-stage hardness and these activated precursors.
  • the curable compositions for the production of the activated precursors are expediently irradiated with actinic light, preferably with radiation having a wavelength of 200 to 600 nm.
  • suitable light sources are xenon lamps, argon lamps, tungsten lamps, carbon arcs, metal halide and metal arc lamps, such as low pressure and medium pressure - And high-pressure mercury lamps or lasers, such as argon or krypton ion lasers.
  • the irradiation is preferably carried out using metal halide or high-pressure mercury lamps.
  • the exposure time depends on various factors, including e.g. the polymerizable organic material, the type of light source and its distance from the irradiated material.
  • the irradiation time is preferably 1 to 60 seconds.
  • the heated compositions can be heated in conventional convection ovens. If short heating or reaction times are required, this can be done by irradiation with, for example, IR radiation, IR lasers or microwave devices.
  • curable compositions according to the invention and the activated precursors obtainable therefrom are suitable, for example, for producing surface coatings on different substrates or as adhesives.
  • Suitable substrates are, for example, metals such as iron, steel, cadmium, zinc and preferably aluminum and copper, semiconductors such as silicon, germanium or GaAs, ceramics, glass, plastics such as thermoplastics, paper or wood and metal-laminated lamates.
  • the hardened products are characterized by good surface adhesion and high flexural strength.
  • a combination of high tensile shear strength with high roller peel strength can be achieved, so that the compositions can be used as structural adhesives.
  • the invention therefore also relates to the cured products obtained from the compositions defined above by direct hot curing or by curing by means of a combined treatment with actinic radiation and heat.
  • the invention further relates to the use of the curable compositions for the purposes mentioned above.
  • Diol and dicarboxylic acid components according to the following table are heated at 180 ° C. for 6 hours and then condensed out under a vacuum of 200 mbar *.
  • the amounts of the components used and the properties of the polyesters produced can be found in the following table:
  • a master formulation of an adhesive is produced with the following recipe:
  • This master formulation is mixed with the respective amounts of the polyester in question and homogenized again in a dissolver for 3-5 minutes.
  • composition of the formulations can be found in the table below.
  • the above adhesives are manually applied to the ends of two Anticorodal -110 test strips of 150x25x1.5 mm, which have been previously roughened and degreased, with a 100 pm spiral doctor.
  • the adhesive layer is activated by irradiation in a minicure device, using a high-pressure mercury vapor lamp of 80 W / cm at a distance of 6-7 cm.
  • the transport speed is 5 m / min, which corresponds to an exposure time of 4.2 s.
  • the two test strips are put together in an aluminum holder (adhesive versus adhesive) so that an adhesive surface of 25 x 12.5 mm is created.
  • the hardening takes place between two heating plates of 100 +/- 2 ° C and a pressure of 0.7 N / mm 2 for 10 minutes. After this time, the holder is removed from the heating plates and cooled for 15 minutes at room temperature. The tensile shear strength (according to DIN 53283) is then measured with a tensile testing machine (tensometer) until the specimen breaks. The tensile shear values given in the table below are the average of 3 bonds.
  • the determination of the roll peel strength of aluminum bonds is carried out after the following handling.
  • test strip each from Avional-150 with the dimensions 25 x 250 x 0.5 mm and 25 x 250 x 2.0 mm is etched in a chromic acid-sulfuric acid bath of the following composition:
  • the parts to be joined are immersed in this etching bath heated to approx. 60-65 ° C for approx. 30 minutes, then under flowing, clear cold water and then under warm water (50- max. 65 ° C) and in the air or in the oven dried at not above 65 ° C.
  • a film is applied manually to the test strips treated in this way using a 60 ⁇ m spiral doctor blade on each side of the test strip.
  • the adhesive films are then exposed as described for the tensile shear strength test.
  • the two test strips are put together in an aluminum gauge so that an adhesive surface of 25 x 200 mm is created.
  • the curing takes place between 2 heating plates of 100 +/- 2 ° C and a pressure of 0.3 N / mm 2 for 10 minutes.
  • the holder is removed from the heating plates and the roll peeling test according to DIN 53289 is carried out at the earliest after the samples have been stored at RT for 24 hours.
  • the values given in the following table are the average of 3 bonds.
  • a master formulation of an adhesive is produced according to the following recipe:

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Abstract

The compositions contain A) an epoxy resin containing an average of at least two 1,2-epoxide groups per molecule or a mixture of these epoxy resins, B) a compound of the formula I or a mixture of these compounds <IMAGE> in which a and b, independently of one another, are 1 or 2, R<1> is a pi - arene, R<2> is a pi -arene, an indenyl anion or a cyclopentadienyl anion, X<-> is an [LQm]<-> radical or an anion of a partially fluorinated or perfluorinated aliphatic or aromatic sulphonic acid, L is B, P, As or Sb, Q is fluorine or some of the radicals Q may alternatively be hydroxyl groups, and m is the valency of L increased by one, and C) a flexible polyester which is terminated by an average of at least two carboxyl groups and is derived from an aliphatic or cycloaliphatic polyol or a mixture of such polyols and an aliphatic, cycloaliphatic or aromatic carboxylic acid or a mixture of such polycarboxylic acids, and can be employed as coating compositions or as adhesives.

Description

Die vorliegende Erfindung betrifft neue Epoxidharzzusammensetzungen, die gehärteten Produkte und die Verwendung der Epoxidharzzusammensetzungen als Klebstoffe oder als Beschichtungsmittel.The present invention relates to new epoxy resin compositions, the cured products and the use of the epoxy resin compositions as adhesives or as coating agents.

Gehärtete Epoxidharze sind im allgemeinen spröde Materialien, die geringe Schälfestigkeiten und Schlagzähigkeiten aufweisen. Um dieser Versprödung entgegenzuwirken, setzt man dem Epoxidharz Flexibilisatoren zu. Beispiele dafür sind elastische Präpolymere, wie Addukte von Epoxidharzen an carboxyl-oder amino-terminierte Butadien/Acrylnitril Copolymere oder carboxyl-terminierte Polyester. Diese Zusätze können zu einer Verschlechterung anderer wünschenswerter Eigenschaften führen, beispielsweise zur Herabsetzung der Zugscherfestigkeit der gehärteten Formulierung. Gemische aus Epoxidharzen und Metallocenkomplexsalzen sind aus der EP-A-94,915 bekannt. Die Gemische können durch Bestrahlung aktiviert werden und in einem thermischen Schritt ausgehärtet werden. Es wurden jetzt Kombinationen von Epoxidharzen, ausgewählten Eisen-Aren-Komplexsalzen und ausgewählten Flexibilisatoren gefunden, aus denen sich Einkomponentenklebstoffe herstellen lassen. Die gehärteten Klebverbindungen aus diesen Gemischen zeichnen sich durch hohe Zugscherfestigkeit und hohe Rollenschälfestigkeit (roller-peel) aus. Ausgewählte Einkomponentenkleber lassen sich bereits bei 80 - 100° C oder tiefer aushärten und beispielsweise als Strukturkleber einsetzen.Hardened epoxy resins are generally brittle materials that have low peel and impact strengths. In order to counteract this embrittlement, flexibilizers are added to the epoxy resin. Examples of this are elastic prepolymers, such as adducts of epoxy resins with carboxyl- or amino-terminated butadiene / acrylonitrile copolymers or carboxyl-terminated polyesters. These additives can degrade other desirable properties, such as lowering the tensile shear strength of the cured formulation. Mixtures of epoxy resins and metallocene complex salts are known from EP-A-94,915. The mixtures can be activated by irradiation and cured in a thermal step. Combinations of epoxy resins, selected iron-arene complex salts and selected flexibilizers have now been found, from which one-component adhesives can be produced. The hardened adhesive bonds from these mixtures are characterized by high tensile shear strength and high roller peel strength (roller peel). Selected one-component adhesives can be cured at 80 - 100 ° C or lower and used, for example, as structural adhesives.

Die vorliegende Erfindung betrifft Zusammensetzungen enthaltend

  • A) ein Epoxidharz mit durchschnittlich mindestens zwei 1,2-Epoxidgruppen pro Molekül oder ein Gemisch dieser Epoxidharze,
  • B) eine Verbindung der Formel I oder ein Gemisch dieser Verbindungen
    Figure imgb0001
    worin a und b unabhängig voneinander 1 oder 2 sind, R1 ein n-Aren ist, R1 ein n-Aren, ein Indenylanion oder ein Cyclopentadienylanion bedeutet, X° ein Anion [LQm] e oder ein Anion einer teil- oder perfluorierten aliphatischen oder aromatischen Sulfonsäure ist, L B, P, As oder Sb bedeutet, Q Fluor ist oder ein Teil der Reste Q auch Hydroxylgruppen sein können und m der um Eins vergrösserten Wertigkeit von L entspricht, und
  • C) einen mit durchschnittlich mindestens zwei Carboxylgruppen terminierten flexiblen Polyester, der sich ableitet von einem aliphatischen oder cycloaliphatischen Polyol oder einem Gemisch solcher Polyole und einer aliphatischen, cycloaliphatischen oder aromatischen Polycarbonsäure oder einem Gemisch solcher Polycarbonsäuren.
The present invention relates to compositions containing
  • A) an epoxy resin with an average of at least two 1,2-epoxy groups per molecule or a mixture of these epoxy resins,
  • B) a compound of formula I or a mixture of these compounds
    Figure imgb0001
     wherein a and b are independently 1 or 2, R 1 is an n-arene, R 1 is an n-arene, an indenyl anion or a cyclopentadienyl anion, X ° is an anion [LQ m] e or an anion of a partially or perfluorinated is aliphatic or aromatic sulfonic acid, means LB, P, As or Sb, Q is fluorine or part of the radicals Q can also be hydroxyl groups and m corresponds to the value of L which is increased by one, and
  • C) a flexible polyester terminated with an average of at least two carboxyl groups, which is derived from an aliphatic or cycloaliphatic polyol or a mixture of such polyols and an aliphatic, cycloaliphatic or aromatic polycarboxylic acid or a mixture of such polycarboxylic acids.

Als Komponente A) eignen sich in der Regel alle Epoxidharze mit durchschnittlich mindestens zwei 1,2-Epoxidgruppen im Molekül. Zu diesen Verbindungen zählen beispielsweise:All epoxy resins with an average of at least two 1,2-epoxy groups in the molecule are generally suitable as component A). These connections include, for example:

I) Polyglycidyl- und Poly-(ß-methylglycidyl)-ester erhältlich durch Umsetzung einer Verbindung mit mindestens zwei Carboxylgruppen im Molekül und Epichlorhydrin bzw. Glycerindichlorhydrin bzw. ß-Methylepichlorhydrin. Die Umsetzung erfolgt zweckmässig in der Gegenwart von Basen.I) Polyglycidyl and poly (β-methylglycidyl) esters obtainable by reacting a compound having at least two carboxyl groups in the molecule and epichlorohydrin or glycerol dichlorohydrin or β-methylepichlorohydrin. The reaction is conveniently carried out in the presence of bases.

Als Verbindung mit mindestens zwei Carboxylgruppen im Molekül können aliphatische, cycloaliphatische oder aromatische Polycarbonsäuren verwendet werden. Beispiele für diese Polycarbonsäuren sind weiter unten als Bildungskomponenten des Polyesters C) aufgeführt.Aliphatic, cycloaliphatic or aromatic polycarboxylic acids can be used as the compound having at least two carboxyl groups in the molecule. Examples of these polycarboxylic acids are listed below as forming components of the polyester C).

11) Polyglycidyl- oder Poly-(ß-methylglycidyl)-ether erhältlich durch Umsetzung einer Verbindung mit mindestens zwei freien alkoholischen Hydroxygruppen und/oder phenolischen Hydroxygruppen und einem geeignet substituierten Epichlorhydrin unter alkalischen Bedingungen, oder in Anwesenheit eines sauren Katalysators und anschliessender Alkalibehandlung.11) Polyglycidyl or poly (β-methylglycidyl) ether obtainable by reacting a compound with at least two free alcoholic hydroxyl groups and / or phenolic hydroxyl groups and a suitably substituted epichlorohydrin under alkaline conditions, or in the presence of an acidic catalyst and subsequent alkali treatment.

Ether dieses Typs leiten sich beispielsweise ab von acyclischen Alkoholen, wie Ethylenglykol, Diethylenglykol und höheren Poly-(oxyethylen)-glykolen, Propan-1,2-diol oder Poly-oxypropylen)-glykolen, Propan-1,3-diol, Butan-1,4-diol, Poly-(oxytetramethylen)-glykolen, Pentan-1,5-diol, Hexan-1,6-diol, Hexan-2.4.6-triol, Glycerin, 1,1,1-Trimethylolpropan, Pentaerythrit, Sorbit, sowie von Polyepichlorhydrinen.Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol or poly-oxypropylene) glycols, propane-1,3-diol, butane 1,4-diol, poly (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerin, 1,1,1-trimethylolpropane, pentaerythritol, Sorbitol and polyepichlorohydrins.

Sie leiten sich aber auch beispielsweise ab von cycloaliphatischen Alkoholen wie 1,3- oder 1,4-Dihydroxycy- c!ohexan, Bis-(4-hydroxycyclohexyl)-methan, 2,2-Bis(4-hydroxycyclohexyl)-propan oder 1,1-Bis-(hydroxymethyl)-cyclohex-3-en.However, they are also derived, for example, from cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane or 1 , 1-bis (hydroxymethyl) cyclohex-3-ene.

Die Epoxidverbindungen können sich auch von einkernigen Phenolen ableiten, wie beispielsweise von Resorcin oder Hydrochinon; oder sie basieren auf mehrkernigen Phenolen wie beispielsweise auf Bis-(4-hydroxyphenyl)-methan, 4,4' Dihydroxydiphenyl, Bis-(4-hydroxyphenyl)-sulfon, 1,1,2,2-Tetrakis-(4-hydroxyphenyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan sowie auf Novolaken erhältlich durch Kondensation von Aldehyden, wie beispielsweise Formaldehyd, Acetaldehyd, Chloral oder Furfuraldehyd mit Phenolen wie Phenol, oder mit Phenolen, die im Kern mit Chloratomen oder C1-CgAlkylgruppen substituiert sind, wie beispielsweise 4-Chlorphenol, 2-Methylphenol oder 4-tert.Butylphenol oder erhältlich durch Kondensation mit Bisphenolen, so wie oben beschrieben.The epoxy compounds can also be derived from mononuclear phenols, such as resorcinol or hydroquinone; or they are based on polynuclear phenols such as, for example, bis (4-hydroxyphenyl) methane, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and on novolaks obtainable by condensation of aldehydes, such as formaldehyde, acetaldehyde , Chloral or furfuraldehyde with phenols such as phenol, or with phenols which are substituted in the core with chlorine atoms or C 1 -C 6 -alkyl groups, such as 4-chlorophenol, 2-methylphenol or 4-tert-butylphe nol or obtainable by condensation with bisphenols, as described above.

III) Poly-(S-glycidyl) Verbindungen, insbesondere Di-S-glycidylderivate, die sich von Dithiolen, wie beispielsweise Ethan-1,2-dithiol oder Bis-(4-merkaptomethylphenyl)-ether ableiten.III) Poly (S-glycidyl) compounds, in particular di-S-glycidyl derivatives, which are derived from dithiols, such as, for example, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.

IV) Cycloaliphatische Epoxidharze, wie Bis-(2,3-epoxicyclopentyl)-ether, 2,3-Epoxicyclopentylglycidylether oder 1,2-Bis-(2,3-epoxycyclopentyloxy)-ethan oder 3,4-Epoxicyclohexylmethyl-3',4'-epoxicyclohexancarbox- ylat.IV) Cycloaliphatic epoxy resins, such as bis (2,3-epoxicyclopentyl) ether, 2,3-epoxicyclopentylglycidyl ether or 1,2-bis (2,3-epoxycyclopentyloxy) ethane or 3,4-epoxicyclohexylmethyl-3 ', 4 '-epoxicyclohexane carboxylate.

Es lassen sich aber auch Epoxidharze verwenden, bei denen die 1,2-Epoxidgruppen an unterschiedliche Heteroatome bzw. funktionelle Gruppen gebunden sind; zu diesen Verbindungen zählen beispielsweise der Glycidylether-glycidylester der Salicylsäure.However, epoxy resins can also be used in which the 1,2-epoxy groups are bonded to different heteroatoms or functional groups; These compounds include, for example, the glycidyl ether glycidyl ester of salicylic acid.

Falls gewünscht, kann eine Mischung von Epoxidharzen in den erfindungsgemässen Gemischen verwendet werden.If desired, a mixture of epoxy resins can be used in the mixtures according to the invention.

Diese Epoxidharze sind an sich bekannt oder können nach bekannten Verfarhen hergestellt werden.These epoxy resins are known per se or can be produced by known processes.

Bei Komponente B) kommen als π-Arene R1 und R2 insbesondere carbocyclisch-aromatische Kohlenwasserstoffe mit 6 bis 24 Kohlenstoffatomen, insbesondere mit 6 bis 12 Kohlenstoffatomen, oder heterocyclisch-aromatische Kohlenwasserstoffe mit 4 bis 11 Kohlenstoffatomen und ein oder zwei S-und/oder O-Atomen in Betracht, wobei diese Gruppen gegebenenfalls durch gleiche oder verschiedene einwertige Reste, wie Halogenatome, vorzugsweise Chlor- oder Bromatome oder Ci-C8-Alkyl, C1-C8-Alkoxy oder Phenyl einfach oder mehrfach, vorzugsweise ein- oder zweifach, substituiert sein können. Diese n-Arengruppen können einkernige, kondensierte mehrkernige oder unkondensierte mehrkernige Systeme darstellen, wobei in den zuletzt genannten Systemen die Kerne direkt oder über Brückenglieder, wie -CH2-, -C(CH3)2-, -O-, -S-, -S02-, -CO- oder -CH=CH-, verknüpft sein können.In component B) come as π-arenes R 1 and R 2 in particular carbocyclic-aromatic hydrocarbons with 6 to 24 carbon atoms, in particular with 6 to 12 carbon atoms, or heterocyclic-aromatic hydrocarbons with 4 to 11 carbon atoms and one or two S and / or O-atoms are suitable, these groups being mono- easy optionally substituted by identical or different monovalent radicals, such as halogen atoms, preferably chlorine or bromine atoms or Ci-C 8 alkyl, C 1 -C 8 alkoxy, or phenyl or polysubstituted, preferably or can be substituted twice. These n-arene groups can be mononuclear, condensed multinuclear or uncondensed multinuclear systems, the nuclei in the latter systems being directly or via bridge members, such as -CH 2 -, -C (CH 3 ) 2 -, -O-, -S- , -S0 2 -, -CO- or -CH = CH-, can be linked.

R2 kann auch ein Indenylanion und insbesondere ein Cyclopentadienylanion sein, wobei auch diese Anionen gegebenenfalls durch gleiche oder verschiedene einwertige Reste, wie oben als Substituenten für n-Arene erwähnt, einfach oder mehrfach, vorzugsweise ein- oder zweifach substituiert sein können.R 2 can also be an indenyl anion and in particular a cyclopentadienyl anion, it also being possible for these anions to be mono- or polysubstituted, preferably mono- or disubstituted, by the same or different monovalent radicals, as mentioned above as substituents for n-arenes.

Die Alkyl- oder Alkoxysubstituenten können dabei geradkettig oder verzweigt sein. Als typische Alkyl- oder Alkoxysubstituenten seien Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.-Butyl, tert.-Butyl, n-Pentyl, n-Hexyl und n-Octyl, Methoxy, Ethoxy, n-Propoxy, Isopropoxy, n-Butoxy, n-Hexyloxy und n-Octyloxy genannt. Dabei sind Alkyl- und Alkoxygruppen mit 1 bis 4 und insbesondere 1 oder 2 Kohlenstoffatomen in den Alkylteilen bevorzugt. Als substituierte π-Arene oder substituierten Indenyl- oder Cyclopentadienylanionen werden solche bevorzugt, die einen oder zwei der obengenannten Substituenten, insbesondere Methyl-, Ethyl-, n-Propyl, Isopropyl, Methoxy-oder Ethoxygruppen, enthalten.The alkyl or alkoxy substituents can be straight-chain or branched. Typical alkyl or alkoxy substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and n-octyl, methoxy, ethoxy, n-propoxy , Called isopropoxy, n-butoxy, n-hexyloxy and n-octyloxy. Alkyl and alkoxy groups with 1 to 4 and in particular 1 or 2 carbon atoms in the alkyl parts are preferred. Preferred substituted π-arenes or substituted indenyl or cyclopentadienyl anions are those which contain one or two of the above-mentioned substituents, in particular methyl, ethyl, n-propyl, isopropyl, methoxy or ethoxy groups.

Als Ri und R2 können gleiche oder verschiedene n-Arene vorliegen.The same or different n-arenes can be present as R i and R 2 .

Beispiele für geeignete n-Arene sind Benzol, Toluol, Xylole, Ethylbenzol, Cumol, Methoxybenzol, Ethoxybenzol, Dimethoxybenzol, p-Chlortoluol, m-Chlortoluol, Chlorbenzol, Brombenzol, Dichlorbenzol, Trimethylbenzol, Trimethoxybenzol, Naphthalin, 1,2-Dihydronaphthalin, 1,2,3,4-Tetrahydronaphthalin, Methylnaphthalin, Methoxynaphthalin, Ethoxynaphthalin, Chlornaphthalin, Bromnaphthalin, Biphenyl, Stilben, Inden, 4,4'-Dimethylbiphenyl, Fluoren, Phenanthren, Anthracen, 9,10-Dihydroanthracen, Triphenyl, Pyren, Perylen, Naphthacen, Coronen, Thiophen, Chromen, Xanthen, Thioxanthen, Benzofuran, Benzothiophen, Naphthothiophen, Thianthren, Diphenylenoxyd und Diphenylensulfid.Examples of suitable n-arenes are benzene, toluene, xylenes, ethylbenzene, cumene, methoxybenzene, ethoxybenzene, dimethoxybenzene, p-chlorotoluene, m-chlorotoluene, chlorobenzene, bromobenzene, dichlorobenzene, trimethylbenzene, trimethoxybenzene, dihydro-naphthalene, naphthalene, 1,2-naphthalene, naphthalene , 2,3,4-tetrahydronaphthalene, methylnaphthalene, methoxynaphthalene, ethoxynaphthalene, chloronaphthalene, bromnaphthalene, biphenyl, stilbene, indene, 4,4'-dimethylbiphenyl, fluorene, phenanthrene, anthracene, 9,10-dihydroanthracene, triphenyl, pyrene, Naphthacene, coronene, thiophene, chromene, xanthene, thioxanthene, benzofuran, benzothiophene, naphthothiophene, thianthrene, diphenylene oxide and diphenylene sulfide.

Beispiele für Anionen substituierter Cyclopentadiene sind die Anionen des Methyl-, Ethyl-, n-Propyl- und n-Butylcyclopentadiens oder die Anionen des Dimethylcyclopentadiens. Bevorzugte Anionen sind das Anion des unsubstituierten Indens und insbesondere des unsubstituierten Cyclopentadiens.Examples of anions of substituted cyclopentadienes are the anions of methyl, ethyl, n-propyl and n-butylcyclopentadiene or the anions of dimethylcyclopentadiene. Preferred anions are the anion of the unsubstituted indene and in particular the unsubstituted cyclopentadiene.

Der Index a ist vorzugsweise 1. Der Index b ist vorzugsweise 1. Wenn a 2 ist, stellt R2 vorzugsweise je das gegebenenfalls substituierte Indenylanion oder insbesondere das Cyclopentadienylanion dar.The index a is preferably 1. The index b is preferably 1. When a is 2, R 2 is preferably each the optionally substituted indenyl anion or in particular the cyclopentadienyl anion.

X° bevorzugt das Anion einer perfluoraliphatischen oder perfluoraromatischen Sulfonsäure und ganz besonders [LQm]°, wie oben definiert.X ° prefers the anion of a perfluoroaliphatic or perfluoroaromatic sulfonic acid and very particularly [LQ m] °, as defined above.

Beispiele für Anionen perfluoraliphatischer oder perfluoraromatischer Sulfonsäuren sind CF3SO

Figure imgb0002
, C2F5SO
Figure imgb0002
, n-C3F7SO
Figure imgb0002
, n-C4F9SO
Figure imgb0002
, n-C6F13SO
Figure imgb0002
, n-C8F17SO
Figure imgb0002
, C6F5SO
Figure imgb0002
und CF3C6F4SO
Figure imgb0002
. Beispiele für besonders bevorzugte Anionen [LQm]° sind PF° , AsF
Figure imgb0010
, SbF
Figure imgb0010
und SbF5(OH)⊖. Ganz besonders bevorzugt werden AsF
Figure imgb0010
, SbF9 und SbF5(OH)⊖ und insbesondere SbF
Figure imgb0010
.Examples of anions of perfluoroaliphatic or perfluoroaromatic sulfonic acids are CF 3 SO
Figure imgb0002
, C 2 F 5 SO
Figure imgb0002
, nC 3 F 7 SO
Figure imgb0002
, nC 4 F 9 SO
Figure imgb0002
, nC 6 F 13 SO
Figure imgb0002
, nC 8 F 17 SO
Figure imgb0002
, C 6 F 5 SO
Figure imgb0002
and CF 3 C 6 F 4 SO
Figure imgb0002
. Examples of particularly preferred anions [LQ m] ° are PF °, AsF
Figure imgb0010
, SbF
Figure imgb0010
and SbF 5 (OH) ⊖. AsF are particularly preferred
Figure imgb0010
, SbF9 and SbF 5 (OH) ⊖ and in particular SbF
Figure imgb0010
.

Härtbare Gemische enthaltend Initiatoren mit diesen ganz besonders bevorzugten Anionen lassen sich nach deren Aktivierung durch Bestrahlung bereits bei niedrigen Temperaturen aushärten.Curable mixtures containing initiators with these very particularly preferred anions can be cured at low temperatures after their activation by irradiation.

Die Verbindungen der Formel 1 sind an sich bekannt oder können in Analogie zu bekannten Verbindungen hergestellt werden. Die Herstellung der Salze mit X- = [LQm]- ist beispielsweise in der EP-A-94,915 beschrieben. Verbindungen der Formel I mit anderen Anionen lassen sich in Abweichung zu den dort beschriebenen Verfahren herstellen, indem man anstelle eines Anions einer komplexen Säure ein anderes Anion der Säure HX in an sich bekannter Weise einführt; dabei besitzt X die oben definierte Bedeutung. Komponente C) kann bei Raumtemperatur fest oder flüssig sein. In der Regel handelt es sich um lineare Polyester oder um Verbindungen mit einem solchen Verzweigungs- oder Vernetzungsgrad, so dass diese sich in einem organischen Lösungsmittel ohne Gelrückstand auflösen lassen. Der Verzweigungs- oder Vernetzungsgrad kann in an sich bekannter Weise durch Funktionalität und Menge polyfunktioneller Kondensationskomponenten (Polyole oder Polycarbonsäuren) geregelt werden.The compounds of formula 1 are known per se or can be prepared analogously to known compounds. The preparation of the salts with X- = [LQ m] - is described for example in EP-A-94,915. Compounds of the formula I with other anions can be produced in deviation from the processes described therein by introducing another anion of the acid HX in a manner known per se instead of an anion of a complex acid; X has the meaning defined above. Component C) can be solid or liquid at room temperature. As a rule, they are linear polyesters or compounds with such a degree of branching or crosslinking that they can be dissolved in an organic solvent without gel residue. The degree of branching or crosslinking can be regulated in a manner known per se by the functionality and amount of polyfunctional condensation components (polyols or polycarboxylic acids).

Die flexiblen Polyester C) können amorph oder teilkristallin sein und sind vorzugsweise mit der Harzkomponente A) verträglich oder leicht darin dispergierbar.The flexible polyesters C) can be amorphous or partially crystalline and are preferably compatible with the resin component A) or easily dispersible therein.

Der Erweichungspunkt der Polyester C) liegt vorzugsweise unterhalb von 100°C.The softening point of the polyester C) is preferably below 100 ° C.

Die Polyester C) besitzen in der Regel Molekulargewichte (Zahlenmittel) von 250 bis 15000, vorzugsweise von 500 bis 2500.The polyesters C) generally have molecular weights (number average) from 250 to 15000, preferably from 500 to 2500.

Ihre Säurezahl beträgt in der Regel 0,1 bis 5 Aequ./kg, vorzugsweise 0,25 bis 2,0 Aequ./kg.Their acid number is generally 0.1 to 5 equivalents / kg, preferably 0.25 to 2.0 equivalents / kg.

Die Viskosität (nach Epprecht) dieser Polyester ist in der Regel kleiner als 2000 mPas (bei 80°C).The viscosity (according to Epprecht) of these polyesters is generally less than 2000 mPas (at 80 ° C).

Die carboxylterminierten flexiblen Polyester leiten sich von aliphatischen oder cycloaliphatischen Polyolen und aliphatischen, cycloaliphatischen oder aromatischen Polycarbonsäuren ab. Bevorzugtes Polyol ist Hexandiol, das gegebenenfalls mit Neopentylglykol oder Cyclohexandimethanol kombiniert wird, um die Hydrolysebeständigkeit zu erhöhen. Bevorzugte Polycarbonsäuren sind α,ω-Dicarbonsäure mit aliphatischen Segmenten wie z.B. Adipin- oder Sebazinsäure.The carboxyl-terminated flexible polyesters are derived from aliphatic or cycloaliphatic polyols and aliphatic, cycloaliphatic or aromatic polycarboxylic acids. The preferred polyol is hexanediol, which is optionally combined with neopentyl glycol or cyclohexanedimethanol in order to increase the resistance to hydrolysis. Preferred polycarboxylic acids are α, ω-dicarboxylic acid with aliphatic segments such as e.g. Adipic or sebacic acid.

Im Fall der Polyole setzt man bevorzugt niedermolekulare und präpolymere Aufbaukomponenten ein.In the case of the polyols, preference is given to using low molecular weight and prepolymeric components.

Unter präpolymeren Aufbaukomponenten versteht man im allgemeinen hydroxyl-terminierte Präpolymere mit wenigstens zwei wiederkehrenden flexibilisierenden Strukturkomponenten. Beispiele dafür sind hydroxyl-terminierte Polyether auf Basis von Polypropylen- und Polybutylenglykol sowie hydroxylterminierte Polycaprolactone. Das Molekulargewicht (Zahlenmittel) dieser Präpolymere beträgt im allgemeinen 150-4000, bevorzugt 500-2500.Prepolymer components are generally understood to mean hydroxyl-terminated prepolymers with at least two recurring flexibilizing structural components. Examples of these are hydroxyl-terminated polyethers based on polypropylene and polybutylene glycol and hydroxyl-terminated polycaprolactones. The number average molecular weight of these prepolymers is generally 150-4000, preferably 500-2500.

Präpolymere Aufbaukomponenten können di- oder höherfunktionell sein, vorzugsweise di- oder trifunktionell. Niedermolekulare Aufbaukomponenten sind in der Regel difunktionell. Polyester C) können aber geringe Mengen niedermolekularer, höherfunktioneller Aufbaukomponenten enthalten.Prepolymeric structural components can be di- or higher-functional, preferably di- or tri-functional. Low molecular weight components are usually difunctional. However, polyester C) can contain small amounts of low-molecular, higher-functional structural components.

Bei allen diesen Ausführungsformen sind Art, Funktionalität und Menge höherfunktioneller Komponenten so zu wählen, dass ein löslicher Polyester mit den oben angegebenen Spezifikationen entsteht. Beispiele für aliphatische Dicarbonsäuren sind gesättigte aliphatische Dicarbonsäuren, wie Oxalsäure, Malonsäure, Bernsteinsäure, a-Methylbernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Azelainsäure, Sebazinsäure oder dimerisierte Linolsäure; oder ungesättigte aliphatische Polycarbonsäuren, wie Maleinsäure, Fumarsäure, Mesaconsäure, Citraconsäure, Glutaconsäure oder Itaconsäure, sowie mögliche Anhydride dieser Säuren.In all of these embodiments, the type, functionality and quantity of more highly functional components are to be selected such that a soluble polyester with the above-mentioned specifications is produced. Examples of aliphatic dicarboxylic acids are saturated aliphatic dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, a-methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid or dimerized linoleic acid; or unsaturated aliphatic polycarboxylic acids, such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, glutaconic acid or itaconic acid, and possible anhydrides of these acids.

Beispiele für cycloaliphatische Dicarbonsäuren sind Hexahydrophthal-, -isophthal- oder -terephthalsäure, Tetrahydrophthal-, -isophthal- oder -terephthalsäure oder 4-Methyltetrahydrophthalsäure, 4-Methylhexahydrophthalsäure oder Endomethylentetrahydrophthalsäure.Examples of cycloaliphatic dicarboxylic acids are hexahydrophthalic, isophthalic or terephthalic acid, tetrahydrophthalic, isophthalic or terephthalic acid or 4-methyltetrahydrophthalic acid, 4-methylhexahydrophthalic acid or endomethylene tetrahydrophthalic acid.

Beispiele für aromatische Dicarbonsäuren sind Phthal-, Isophthal-und Terephthalsäure.Examples of aromatic dicarboxylic acids are phthalic, isophthalic and terephthalic acid.

Beispiele für höherfunktionelle Carbonsäuren sind aromatische Tri-oder Tetracarbonsäuren, wie Trimellitsäure, Trimesinsäure, Pyromellitsäure oder Benzophenontetracarbonsäure; oder trimerisierte Fettsäuren oder Gemische von dimerisierten und trimerisierten Fettsäuren, wie sie beispielsweise unter der Bezeichnung Pripo10 im Handel sind.Examples of higher functional carboxylic acids are aromatic tricarboxylic or tetracarboxylic acids, such as trimellitic acid, trimesic acid, pyromellitic acid or benzophenonetetracarboxylic acid; or trimerized fatty acids or mixtures of dimerized and trimerized fatty acids, as are commercially available, for example, under the name Pripo1 0 .

Beispiele für niedermolekulare aliphatische Diole sind α,ω-Alkylendiole, wie Ethylenglykol, Propan-1,2-diol, Propan-1,3-diol, Butan-1,4-diol, Pentan-1,5-diol, Neopentylglykol, Hexan-1,6-diol, Octan-1,8-diol, Decan-3,10-diol oder Dodecan-1,12-diol.Examples of low molecular weight aliphatic diols are α, ω-alkylene diols, such as ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, neopentyl glycol, hexane -1,6-diol, octane-1,8-diol, decane-3,10-diol or dodecane-1,12-diol.

Beispiele für niedermolekulare cycloaliphatische Diole sind 1,3-oder 1,4-Dihydroxycyclohexan, 1,4-Cyclohexandimethanol, Bis-(4-hydroxycyclohexyl)-methan oder 2,2-Bis-(4-hydroxycyclohexyl)-propan.Examples of low molecular weight cycloaliphatic diols are 1,3- or 1,4-dihydroxycyclohexane, 1,4-cyclohexane dimethanol, bis (4-hydroxycyclohexyl) methane or 2,2-bis (4-hydroxycyclohexyl) propane.

Beispiele für niedermolekulare höherfunktionnelle Alkohole sind 1,1,1-Trimethylolethan, 1,1,1-Trimethylolpropan, Glycerin oder Pentaerithrit.Examples of low molecular weight higher functional alcohols are 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerin or pentaerythritol.

Beispiele für geeignete hydroxyl-terminierte Präpolymere mit mindestens zwei wiederkehrenden flexibilisierenden Struktureinheiten sind Polyether, Polyester oder Polythioether, sofern diese Verbindungen hydroxyl-terminiert sind.Examples of suitable hydroxyl-terminated prepolymers with at least two recurring flexibilizing structural units are polyethers, polyesters or polythioethers, provided that these compounds are hydroxyl-terminated.

Diese Verbindungen sind dem Fachmann an sich bekannt. Sie können linear oder verzweigt sein; bevorzugt werden die linearen Typen.These compounds are known per se to the person skilled in the art. They can be linear or branched; the linear types are preferred.

Beispiele für hydroxyl-terminierte Polyether sind Polyalkylenetherpolyole, die durch ionische Polymerisation. Copolymerisation oder Blockcopolymerisation von Alkylenoxiden, wie Ethylenoxid, Propylenoxid oder Butylenoxid, gegebenenfalls in Gegenwart von di- oder polyfunktionnellen Alkoholen, wie Butan-1,4-diol, 1,1,1-Trimethylolethan, 1,1,1-Trimethylolpropan, Hexan-1,2,6-triol, Glycerin, Pentaerithrit oder Sorbit, oder von Aminen, wie Methylamin, Ethylendiamin oder Hexan-1,6-diamin, oder durch ionische Polymerisation oder Copolymerisation cyclischer Ether, wie Tetrahydrofuran, Ethylenoxid oder Propylenoxid mit sauren Katalysatoren, wie BFa·Etherat oder durch Polykondensation von unter Wasserabspaltung polykondensierbaren Glykolen, wie Hexan-1,6-diol, in Gegenwart saurer Veretherungskatalysatoren, wie p-Toluolsulfonsäure, erhalten werden. Ferner kann man auch Oxalkylierungsprodukte von Phosphorsäure oder phosphoriger Säure mit Ethylenoxid, Propylenoxid oder Butylenoxid verwenden.Examples of hydroxyl-terminated polyethers are polyalkylene ether polyols which are produced by ionic polymerization. Copolymerization or block copolymerization of alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, optionally in the presence of di- or polyfunctional alcohols, such as butane-1,4-diol, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, hexane 1,2,6-triol, glycerol, pentaerithritol or sorbitol, or of amines, such as methylamine, ethylenediamine or hexane-1,6-diamine, or by ionic polymerization or copolymerization of cyclic ethers, such as tetrahydrofuran, ethylene oxide or propylene oxide with acidic catalysts, such as BF a · etherate or by polycondensation of glycols which are polycondensable under elimination of water, such as hexane-1,6-diol, in the presence of acidic etherification catalysts, such as p-toluenesulfonic acid. It is also possible to use oxyalkylation products of phosphoric acid or phosphorous acid with ethylene oxide, propylene oxide or butylene oxide.

Beispiele für hydroxyl-terminierte Polyesterpolyole sind Verbindungen, die sich von Di- und/oder Polycarbonsäuren und Di-und/oder Polyolen, bevorzugt von Dicarbonsäuren und Diolen ableiten. Beispiele für geeignete Polyole und Polycarbonsäuren sind weiter oben als Aufbaukomponenten für die Polyester C) aufgezählt.Examples of hydroxyl-terminated polyester polyols are compounds which are derived from di- and / or polycarboxylic acids and di- and / or polyols, preferably from dicarboxylic acids and diols. Examples of suitable polyols and polycarboxylic acids are listed above as structural components for the polyesters C).

Weitere Beispiele für geeignete hydroxyl-terminierte Präpolymere sind Polymerisationsprodukte von Lactonen, beispielsweise von s-Caprolactonen; oder Polyalkylenthioetherpolyole, beispielsweise die Polykondensationsprodukte des Thiodiglykols mit sich und mit Diolen und/oder Polyolen, wie beispielsweise Hexan-1,6-diol, Triethylenglykol, 2,2-Dimethyl-1,3-propandiol oder 1,1,1-Trimethylolpropan.Further examples of suitable hydroxyl-terminated prepolymers are polymerization products of lactones, for example of s-caprolactones; or polyalkylene thioether polyols, for example the polycondensation products of thiodiglycol with and with diols and / or polyols, such as, for example, hexane-1,6-diol, triethylene glycol, 2,2-dimethyl-1,3-propanediol or 1,1,1-trimethylolpropane.

Die Herstellung der Polyester C) erfolgt in an sich bekannter Weise durch Umsetzung der Polyolkomponente(n) mit einem Ueberschuss an Polycarbonsäurekomponente(n). Anstelle der Polycarbonsäure kann man auch ein polyesterbildendes Derivat einsetzen, beispielsweise ein Anhydrid.The polyester C) is prepared in a manner known per se by reacting the polyol component (s) with an excess of polycarboxylic acid component (s). Instead of the polycarboxylic acid you can also use a polyester-forming derivative, for example an anhydride.

Bei einer anderen Herstellungsweise kondensiert man Polyol und Polycarbonsäure(derivat), wobei das Polyol im Ueberschuss eingesetzt wird. Das entstandene Präpolymere mit Hydroxylgruppen wird dann mit Carbonsäureanhydriden zum carboxyl-terminierten Polyester verkappt.In another production method, polyol and polycarboxylic acid (derivative) are condensed, the polyol being used in excess. The resulting prepolymer with hydroxyl groups is then capped with carboxylic acid anhydrides to give the carboxyl-terminated polyester.

Man kann auch von den anderen, weiter oben beschriebenen hydroxylterminierten Präpolymeren ausgehen, und diese mit geeigneten Carbonsäureanhydriden verkappen.It is also possible to start from the other hydroxyl-terminated prepolymers described above and to cap them with suitable carboxylic anhydrides.

Die Polyesterharze können durch allgemeine Arbeitsweisen, die bei der Herstellung solcher Harze Anwendung finden, hergestellt werden. So kann man zweckmässigerweise die Veresterung durch Schmelzkondensation der Carbonsäurekomponente(n) und des Diols durchführen. Die Reaktionsteilnehmer werden dabei beispielsweise unter Rühren auf Temperaturen bis zu 250°C erhitzt. Dabei kann es sich anbieten, ein inertes Gas, wie beispielsweise Stickstoff, durch die Reaktionsmischung zu leiten, um das während der Veresterungsreaktion gebildete Wasser zu entfernen. Auch kann am Ende der Veresterungsreaktion gegebenenfalls ein leichtes Vakuum angelegt werden, um restliche niedermolekulare Spaltprodukte zu isolieren. Der bevorzugte Temperaturbereich der Schmelzkondensation beträgt 160-250° C. Man kann aber auch andere Formen der Polykondensation anwenden, beispielsweise die Grenzflächenpolykondensation, die Polykondensation in Lösung, in Suspension oder in Masse.The polyester resins can be made by general procedures used in the manufacture of such resins. For example, the esterification can conveniently be carried out by melt condensation of the carboxylic acid component (s) and the diol. The reactants are heated, for example, to temperatures up to 250 ° C. with stirring. It may be advisable to pass an inert gas, such as nitrogen, through the reaction mixture in order to remove the water formed during the esterification reaction. At the end of the esterification reaction, a slight vacuum can optionally also be applied in order to isolate residual low-molecular cleavage products. The preferred temperature range for the melt condensation is 160-250 ° C. However, other forms of polycondensation can also be used, for example interfacial polycondensation, polycondensation in solution, in suspension or in bulk.

Die Kondensation von Polycarbonsäuren und/oder Polyolen mit Funktionalitäten grösser als zwei erfolgt in dem Fachmann an sich bekannter Weise unter Bedingungen und mit stöchiometrischen Verhältnissen, so dass eine Gelierung verhindert und eine Verzweigung des Polyesters bewirkt wird.The condensation of polycarboxylic acids and / or polyols with functionalities greater than two takes place in a manner known per se to the person skilled in the art under conditions and with stoichiometric ratios, so that gelation is prevented and the polyester is branched.

Bei dem Polyester C) kann es sich um ein carboxyl-terminiertes Präpolymeres handeln oder dieses Addukt liegt im Gemisch mit nicht umgesetzter Carbonsäure oder Anhydrid vor.The polyester C) can be a carboxyl-terminated prepolymer or this adduct is present in a mixture with unreacted carboxylic acid or anhydride.

Bevorzugte Komponenten A) sind Polyglycidylether auf der Basis von Phenolen und ganz besonders die Diglycidylether von Bisphenolen.Preferred components A) are polyglycidyl ethers based on phenols and very particularly the diglycidyl ethers of bisphenols.

Diese Harze können flüssig oder fest sein. Für Klebstoffe verwendet man bevorzugt Kombinationen von flüssigen Diglycidylethern auf Bisphenol-Basis mit festen Diglycidylethern auf Bisphenol-Basis oder mit festen Polyglycidylethern auf Basis von Phenol-Formaldehyd-Novolaken oder Kresol-Formaldehyd Novolaken. Besonders bevorzugt werden die Kombinationen von flüssigen und festen Bisphenol-A-Diglycidylethern.These resins can be liquid or solid. Combinations of liquid bisphenol-based diglycidyl ethers with solid bisphenol-based diglycidyl ethers or with solid polyglycidyl ethers based on phenol-formaldehyde novolaks or cresol-formaldehyde novolaks are preferably used for adhesives. The combinations of liquid and solid bisphenol A diglycidyl ethers are particularly preferred.

Bevorzugte Komponenten B) sind Verbindungen der Formel 1, wie oben definiert, worin Rl ein ein-oder zweifach alkyl- oder alkoxysubstituierter Benzol- oder Naphthalinrest ist, R2 ein Cyclopentadienylanion ist und X⊖SbF

Figure imgb0014
bedeutet.Preferred components B) are compounds of the formula 1, as defined above, in which R 1 is a mono- or di-alkyl or alkoxy-substituted benzene or naphthalene radical, R 2 is a cyclopentadienyl anion and X ⊖ SbF
Figure imgb0014
means.

Bevorzugte Substituenten des Benzol- oder Naphthalinrestes sind Ci-Cs-Alkyl- oder -Alkoxyreste, insbesondere Methyl, Ethyl, n-Propyl oder Isopropyl, Methoxy, Ethoxy, n-Propoxy oder Isopropoxy. Bevorzugte Komponenten C) sind Verbindungen der Formel II

Figure imgb0015
worin R3 ein Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure nach dem Entfernen der Carboxylgruppen ist, bevorzugt ein Rest einer aliphatischen Dicarbonsäure, insbesondere ein Rest der Fumarsäure oder der Maleinsäure, R4 ein Rest eines zweiwertigen aliphatischen oder cycloaliphatischen Alkohols nach dem Entfernen der Hydroxylgruppen ist und c eine ganze Zahl von 1 bis 50 bedeutet.Preferred substituents of the benzene or naphthalene radical are Ci-Cs-alkyl or alkoxy radicals, in particular methyl, ethyl, n-propyl or isopropyl, methoxy, ethoxy, n-propoxy or isopropoxy. Preferred components C) are compounds of the formula II
Figure imgb0015
 wherein R 3 is a residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after removal of the carboxyl groups, preferably a residue of an aliphatic dicarboxylic acid, in particular a residue of fumaric acid or maleic acid, R 4 is a residue of a dihydric aliphatic or cycloaliphatic alcohol after removal of the hydroxyl groups and c is an integer from 1 to 50.

Der Index c ist vorzugsweise 2 bis 25.The index c is preferably 2 to 25.

Besonders bevorzugte Komponenten C) sind Verbindungen der Formel 11, worin zumindest ein Teil der Reste R4 zweiwertige Reste eines Polyalkylenethers sind.Particularly preferred components C) are compounds of the formula 11 in which at least some of the R 4 radicals are divalent radicals of a polyalkylene ether.

Zu ganz besonders bevorzugten Resten R4 zählen die Gruppen der Formeln lila, Illb und insbesondere IIIc

Figure imgb0016
Figure imgb0017
Figure imgb0018
worin r eine ganze Zahl von 4 bis 25 ist.Very particularly preferred radicals R 4 include the groups of the formulas lilac, Illb and in particular IIIc
Figure imgb0016
Figure imgb0017
Figure imgb0018
 where r is an integer from 4 to 25.

Die härtbaren Zusammensetzungen können auch weitere, bekannte und üblicherwiese in der Technik photopolymerisierbarer Materialien oder der Klebstoffe eingesetzte Zusatzstoffe D) enthalten. Beispiele für solche Zusatzstoffe sind Pigmente, Farbstoffe, Füllstoffe und Verstärkungsmittel, Glasfasern und sonstige Fasern, Flammhemmstoffe, Antistatika, Verlaufmittel, Antioxydantien, Haftvermittler, Weichmacher, Netzmittel, Thixotropiemittel und Lichtschutzmittel.The curable compositions can also contain other known and customary additives D) used in the art of photopolymerizable materials or adhesives. Examples of such additives are pigments, dyes, fillers and reinforcing agents, glass fibers and other fibers, flame retardants, antistatic agents, leveling agents, antioxidants, adhesion promoters, plasticizers, wetting agents, thixotropic agents and light stabilizers.

Die erfindungsgemässen Zusammensetzungen können auch Kombinationen von Initiatoren der Formel I und Sensibilisatoren enthalten. Insbesondere bei Verbindungen der Formel I, worin R1 ein gegebenenfalls substituiertes Benzolderivat ist, beobachtet man bei Zugabe von Sensibilisatoren in der Regel eine Steigerung der Lichtempfindlichkeit. Beispiele für geeignete Sensibilisatoren findet man in der EP-A-152,377. Ferner können in den erfindungsgemässen Zusammensetzungen auch Kombinationen von Initiatoren der Formel I, Oxidationsmitteln und gegebenenfalls Sensibilisatoren für die Verbindungen I eingesetzt werden. Oxidationsmittel setzen in der Regel die Härtungstemperaturen herab und gestatten eine Verarbeitung unter milden Bedingungen. Geeignete Oxidationsmittel sind in der EP-A-126,712 erwähnt.The compositions according to the invention can also contain combinations of initiators of the formula I and sensitizers. In particular in the case of compounds of the formula I in which R 1 is an optionally substituted benzene derivative, an increase in photosensitivity is generally observed when sensitizers are added. Examples of suitable sensitizers can be found in EP-A-152,377. Combinations of initiators of the formula I, oxidizing agents and, if appropriate, sensitizers for the compounds I can also be used in the compositions according to the invention. Oxidizing agents usually lower the curing temperatures and allow processing under mild conditions. Suitable oxidizing agents are mentioned in EP-A-126,712.

Die folgenden Mengenangaben beziehen sich jeweils auf die Gesamtmenge an Komponenten A), B), C) und D).The following quantities refer to the total amount of components A), B), C) and D).

Die Menge an Komponente A) beträgt in der Regel 40 - 95 Gew.9/o, insbesondere 50 - 90 Gew.%. Der Initiator B) liegt in der Regel in Mengen von 0,1 -10 Gew.%, insbesondere von 0,1 bis 5 Gew.%, vor. Der Anteil von Komponente C) beträgt in der Regel 5 bis 50 Gew.%, besonders 5 bis 30 Gew.%, und ganz besonders bevorzugt 10 bis 30 Gew.%, während der Anteil der Zusatzstoffe D) 0 - 50 Gew.% ausmachen kann.The amount of component A) is generally 40-95% by weight, in particular 50-90% by weight. The Initiator B) is generally present in amounts of 0.1-10% by weight, in particular 0.1 to 5% by weight. The proportion of component C) is generally 5 to 50% by weight, particularly 5 to 30% by weight, and very particularly preferably 10 to 30% by weight, while the proportion of additives D) makes up 0 to 50% by weight can.

Die erfindungsgemässen härtbaren Zusammensetzungen sind lichtempfindlich. Sie lassen sich in beliebiger Form erhalten, z.B. als homogene flüssige oder feste Gemische. Feste Produkte können in an sich bekannter Weise zum Beispiel durch Verflüssigung fester Epoxidharze gegebenenfalls unter Zusatz geeigneter Lösungsmittel im Dunkeln oder unter rotem Licht, Erhitzen auf Temperaturen über ihrem Glasübergangspunkt, Zugabe des Initiators B) und der Komponente C), Homogenisierung und Abkühlung der entstandenen Gemische erhalten werden. Gewünschtenfalls kann man die so erhaltenen Produkte anschliessend zerkleinern. Im Falle von flüssigen Epoxidharzen kann die erfindungsgemässe Zusammensetzung durch einfaches Vermischen der Komponenten erhalten werden.The curable compositions according to the invention are sensitive to light. They can be obtained in any form, e.g. as homogeneous liquid or solid mixtures. Solid products can be prepared in a manner known per se, for example by liquefying solid epoxy resins, if appropriate with the addition of suitable solvents in the dark or under red light, heating to temperatures above their glass transition point, addition of initiator B) and component C), homogenization and cooling of the resulting mixtures be preserved. If desired, the products thus obtained can then be comminuted. In the case of liquid epoxy resins, the composition according to the invention can be obtained by simply mixing the components.

Die erfindungsgemässen härtbaren Zusammensetzungen sind bei Raumtemperatur in verhältnismässiger Dunkelheit, z.B. in rotem Licht, beträchtliche Zeit lagerfähig. Je nach ihrer Zusammensetzung und ihrem Endzweck, z.B. zur Herstellung von Ueberzügen oder Filmen, können sie direkt thermisch gehärtet werden oder in zwei Stufen durch eine Kombination von Bestrahlung und Erhitzen. Die Härtungstemperatur beträgt im allgemeinen 40 - 200° C, bevorzugt 80 - 150° C, besonders bevorzugt 80 - 110° C.The curable compositions of the invention are at room temperature in relatively dark, e.g. in red light, storable for considerable time. Depending on their composition and their end purpose, e.g. for the production of coatings or films, they can be thermally hardened directly or in two stages by a combination of radiation and heating. The curing temperature is generally 40-200 ° C., preferably 80-150 ° C., particularly preferably 80-110 ° C.

Besonders bevorzugt wird die zweistufige Polymerisation (Härtung), indem man zunächst den Initiator der Formel durch Bestrahlung des härtbaren Gemisches aktiviert und dann die so erhaltenen aktivierten Vorstufen thermisch härtet, wobei die Bestrahlungstemperatur unter der zum nachfolgenden Heisshärten angewandten liegt. Diese aktivierten Vorstufen lassen sich normalerweise bei Temperaturen härten, die erheblich niedriger liegen als bei Abwesenheit von Komponente C) erforderlich wäre, vorzugsweise bei Temperaturen zwischen 80 und 110°C. Diese zweistufige Härtung ermöglicht es auch, die Polymerisation auf besonders einfache und vorteilhafte Weise zu steuern. Zudem sind die aus den erfindungsgemässen härtbaren Zusammensetzungen erhältlichen aktivierten Vorstufen in der Regel bei Raumtemperatur sogar im Licht beträchtliche Zeit lagerfähig, dies trifft besonders auf diejenigen Gemische zu, welche als Komponente A) ein hochviskoses oder festes Epoxidharz enthalten. Dieses Merkmal stellt einen weiteren wesentlichen Vorteil der zweistufigen Härtig und dieser aktivierten Vorstufen dar.Two-stage polymerization (curing) is particularly preferred by first activating the initiator of the formula by irradiating the curable mixture and then thermally curing the activated precursors thus obtained, the irradiation temperature being below that used for subsequent hot curing. These activated precursors can normally be cured at temperatures which are considerably lower than would be required in the absence of component C), preferably at temperatures between 80 and 110 ° C. This two-stage curing also makes it possible to control the polymerization in a particularly simple and advantageous manner. In addition, the activated precursors obtainable from the curable compositions according to the invention can generally be stored for a considerable time even at room temperature, in particular in the case of mixtures which contain, as component A), a highly viscous or solid epoxy resin. This feature represents another significant advantage of the two-stage hardness and these activated precursors.

Die Bestrahlung der härtbaren Zusammensetzungen zur Herstellung der aktivierten Vorstufen erfolgt zweckmässig mit aktinischem Licht, vorzugsweise mit Strahlung einer Wellenlänge von 200 bis 600 nm. Als Lichtquellen eignen sich beispielsweise Xenonlampen, Argonlampen, Wolframlampen, Kohlelichtbögen, Metallhalogenid- und Metallichtbogenlampen, wie Niederdruck-, Mitteldruck- und Hochdruckquecksilberlampen oder auch Laser, wie Argon- oder Kryptonionen-Laser. Vorzugsweise wird die Bestrahlung mit Metallhalogenid- oder Hochdruckquecksilberlampen durchgeführt. Die Bestrahlungszeit hängt von verschiedenen Faktoren ab, einschliesslich z.B. dem polymerisierbaren organischen Material, der Art der Lichtquelle und deren Abstand vom bestrahlten Material. Die Bestrahlungszeit beträgt vorzugsweise 1 bis 60 Sekunden. Das Erwärmen der belichteten Zusammensetzungen kann in herkömmlichen Konvektionsöfen stattfinden. Sind kurze Erwärmungs- oder Reaktionszeiten erforderlich, so kann dies durch Bestrahlung mit beispielsweise IR-Strahlung, IR-Lasern oder Mikrowellengeräten erfolgen.The curable compositions for the production of the activated precursors are expediently irradiated with actinic light, preferably with radiation having a wavelength of 200 to 600 nm. Examples of suitable light sources are xenon lamps, argon lamps, tungsten lamps, carbon arcs, metal halide and metal arc lamps, such as low pressure and medium pressure - And high-pressure mercury lamps or lasers, such as argon or krypton ion lasers. The irradiation is preferably carried out using metal halide or high-pressure mercury lamps. The exposure time depends on various factors, including e.g. the polymerizable organic material, the type of light source and its distance from the irradiated material. The irradiation time is preferably 1 to 60 seconds. The heated compositions can be heated in conventional convection ovens. If short heating or reaction times are required, this can be done by irradiation with, for example, IR radiation, IR lasers or microwave devices.

Die erfindungsgemässen härtbaren Zusammensetzungen und die daraus erhältlichen aktivierten Vorstufen eignen sich beispielsweise zur Herstellung von Oberflächenbeschichtungen auf unterschiedlichen Substraten oder als Klebstoffe.The curable compositions according to the invention and the activated precursors obtainable therefrom are suitable, for example, for producing surface coatings on different substrates or as adhesives.

Geeignete Substrate sind beispielsweise Metalle, wie Eisen, Stahl, Cadmium, Zink und bevorzugt Aluminium und Kupfer, Halbleiter, wie Silizium, Germanium oder GaAs, Keramik, Glas, Kunststoffe wie Thermoplaste, Papier oder Holz und metallkaschierte Lamiate.Suitable substrates are, for example, metals such as iron, steel, cadmium, zinc and preferably aluminum and copper, semiconductors such as silicon, germanium or GaAs, ceramics, glass, plastics such as thermoplastics, paper or wood and metal-laminated lamates.

Die gehärteten Produkte zeichnen sich durch gute Oberflächenhaftung und hohe Biegefestigkeit aus. Bei Verklebungen lässt sich eine Kombination von hoher Zugscherfestigkeit mit hoher Rollenschälfestigkeit erzielen, so dass sich die Zusammensetzungen als Strukturkleber einsetzen lassen.The hardened products are characterized by good surface adhesion and high flexural strength. When bonding, a combination of high tensile shear strength with high roller peel strength can be achieved, so that the compositions can be used as structural adhesives.

Die Erfindung betrifft daher auch die gehärteten Produkte aus den oben definierten Zusammensetzungen erhältlich durch direkte Heisshärtung oder durch Härtung mittels einer kombinierten Behandlung mit aktinischer Strahlung und Wärme.The invention therefore also relates to the cured products obtained from the compositions defined above by direct hot curing or by curing by means of a combined treatment with actinic radiation and heat.

Ferner betrifft die Erfindung die Verwendung der härtbaren Zusammensetzungen für die oben erwähnten Zwecke.The invention further relates to the use of the curable compositions for the purposes mentioned above.

Die folgenden Beispiele erläutern die Erfindung.The following examples illustrate the invention.

A) Herstellung der carboxyl-terminierten PolyesterA) Preparation of the carboxyl-terminated polyester

Allgemeine Arbeitsvorschrift:General working instructions:

Diol- und Dicarbonsäurekomponenten gemäss der folgenden Tabelle werden 6 Stunden bei 180°C erhitzt und anschliessend unter Anlegen eines Vakuums von 200 mbar auskondensiert*. Die Mengen der eingesetzten Komponenten und die Eigenschaften der hergestellten Polyester findet man in der folgenden Tabelle:Diol and dicarboxylic acid components according to the following table are heated at 180 ° C. for 6 hours and then condensed out under a vacuum of 200 mbar *. The amounts of the components used and the properties of the polyesters produced can be found in the following table:

(*Polyester I: 2 h bei 180°C;

  • Polyester II - VIII: 0,5 h bei 210°C;
  • Polyester IX: 2 h bei 210°C;
( * Polyester I: 2 h at 180 ° C;
  • Polyester II - VIII: 0.5 h at 210 ° C;
  • Polyester IX: 2 h at 210 ° C;

Polyester X - XII: 1 h bei 210°C.)

Figure imgb0019
Figure imgb0020
 Polyester X - XII: 1 h at 210 ° C.)
Figure imgb0019
Figure imgb0020

B) Herstellung und Test von KlebstofformulierungenB) Manufacture and test of adhesive formulations

Es wird eine Stammformulierung eines Klebstoffes mit folgender Rezeptur hergestellt:

Figure imgb0021
A master formulation of an adhesive is produced with the following recipe:
Figure imgb0021

Diese Komponenten werden in einer lichtundurchlässigen PE-Flasche mit einem Dissolver bei einer Geschwindigkeit von 10'000 RPM bis maximal 70°C während höchstens 10' homogenisiert.These components are homogenized in an opaque PE bottle with a dissolver at a speed of 10,000 RPM up to a maximum of 70 ° C for a maximum of 10 '.

Diese Stammformulierung wird mit den jeweiligen Mengen des betreffenden Polyesters versetzt und nochmals im Dissolver während 3-5 Minuten homogenisiert.This master formulation is mixed with the respective amounts of the polyester in question and homogenized again in a dissolver for 3-5 minutes.

Die Zusammensetzung der Formulierungen entnimmt man der untenstehenden Tabelle.The composition of the formulations can be found in the table below.

Untersuchung der Zugscherfestigkeit:Investigation of tensile shear strength:

Zur Bestimmung der Zugscherfestigkeit von Aluminiumverklebungen werden obige Klebstoffe manuell mit einer 100 pm Spiralrakel auf die Enden zweier Anticorodal -110 Prüfstreifen von 150x25x1,5 mm, welche vorgängig aufgerauht und entfettet wurden, appliziert. Die Klebstoffschicht wird durch Bestrahlung in einem Minicure-Gerät aktiviert, wobei einen Hochdruck-Quecksilberdampflampe von 80 W/cm in einem Abstand von 6-7 cm verwendet wird. Die Transportgeschwindigkeit beträgt 5m/min, was einer Belichtungszeit von 4,2 s entspricht. Nach der Bestrahlung werden die beiden Prüfstreifen in einer Alu-Halterung so zusammengefügt (Klebstoff gegen Klebstoff), dass eine Klebefläche von 25 x 12,5 mm entsteht. Die Härtig erfolgt zwischen zwei Heizplatten von jeweils 100 +/- 2°C und einem Druck von 0,7 N/mm2 während 10 Min. Nach dieser Zeit wird die Halterung den Heizplatten entnommen und während 15 Minuten bei Raumtemperatur abgekühlt. Anschliessend wird mit einer Zugprüfmaschine (Tensometer) die Zugscherfestigkeit (gemäss DIN 53283) bis zum Bruch des Prüflings gemessen. Die in der untenstehenden Tabelle angegebenen Zugscherwerte sind jeweils das Mittel aus 3 Verklebungen.To determine the tensile shear strength of aluminum bonds, the above adhesives are manually applied to the ends of two Anticorodal -110 test strips of 150x25x1.5 mm, which have been previously roughened and degreased, with a 100 pm spiral doctor. The adhesive layer is activated by irradiation in a minicure device, using a high-pressure mercury vapor lamp of 80 W / cm at a distance of 6-7 cm. The transport speed is 5 m / min, which corresponds to an exposure time of 4.2 s. After the irradiation, the two test strips are put together in an aluminum holder (adhesive versus adhesive) so that an adhesive surface of 25 x 12.5 mm is created. The hardening takes place between two heating plates of 100 +/- 2 ° C and a pressure of 0.7 N / mm 2 for 10 minutes. After this time, the holder is removed from the heating plates and cooled for 15 minutes at room temperature. The tensile shear strength (according to DIN 53283) is then measured with a tensile testing machine (tensometer) until the specimen breaks. The tensile shear values given in the table below are the average of 3 bonds.

Untersuchung der Rollenschälfestigkeit (roller-peel):Investigation of roller peel strength:

Die Bestimmung der Rollenschälfestigkeit von Aluminiumverklebungen wird nach folgender Handhabung ausgeführt.The determination of the roll peel strength of aluminum bonds is carried out after the following handling.

Je ein Prüfstreifen aus Avional-150 mit den Dimensionen 25 x 250 x 0,5 mm und 25 x 250 x 2,0 mm werden in einem Chromsäureschwefelsäurebad folgender Zusammensetzung geätzt:

Figure imgb0022
One test strip each from Avional-150 with the dimensions 25 x 250 x 0.5 mm and 25 x 250 x 2.0 mm is etched in a chromic acid-sulfuric acid bath of the following composition:
Figure imgb0022

Die Fügeteile werden in dieses auf ca. 60-65° C angewärmte Aetzbad ca. 30 Minuten eingetaucht, anschliessend unter fliessendem, klarem kalten Wasser un dann unter warmem Wasser (50- max. 65°C) gespült und an der Luft oder im Ofen bei nicht über 65°C getrocknet.The parts to be joined are immersed in this etching bath heated to approx. 60-65 ° C for approx. 30 minutes, then under flowing, clear cold water and then under warm water (50- max. 65 ° C) and in the air or in the oven dried at not above 65 ° C.

Auf die so behandelten Prüfstreifen wird manuell mit einer 60 µm Spiralrakel auf je 1 Seite des Prüfstreifens ein Film appliziert. Die Anschliessende Belichtung der Klebefilme erfolgt wie bei der Prüfung der Zugscherfestigkeit beschrieben.A film is applied manually to the test strips treated in this way using a 60 µm spiral doctor blade on each side of the test strip. The adhesive films are then exposed as described for the tensile shear strength test.

Nach der Bestrahlung werden die beiden Prüfstreifen in einer Alu-Lehre so zusammengefügt, dass eine Klebefläche von 25 x 200 mm entsteht. Die Härtung erfolgt zwischen 2 Heizplatten von jeweils 100 +/- 2°C und einem Druck von 0,3 N/mm2 während 10 Minuten. Nach dieser Zeit wird die Halterung den Heizplatten entnommen und frühestens nach 24 h Lagerung der Proben bei RT der Rollenschälversuch nach DIN 53289 ausgeführt. Die in der folgenden Tabelle angegebenen Werte sind jeweils das Mittel aus 3 Verklebungen.

Figure imgb0023
After the irradiation, the two test strips are put together in an aluminum gauge so that an adhesive surface of 25 x 200 mm is created. The curing takes place between 2 heating plates of 100 +/- 2 ° C and a pressure of 0.3 N / mm 2 for 10 minutes. After this time, the holder is removed from the heating plates and the roll peeling test according to DIN 53289 is carried out at the earliest after the samples have been stored at RT for 24 hours. The values given in the following table are the average of 3 bonds.
Figure imgb0023

Beispiele 28 - 30: Tests von KlebstofformulierungenExamples 28-30: Tests on adhesive formulations

Es wird eine Stammformulierung eins Klebstoffes nach folgender Rezeptur hergestellt:

Figure imgb0024
A master formulation of an adhesive is produced according to the following recipe:
Figure imgb0024

Als Photoinitiator verwendet man (η6-Cumol) (η5 cyclopentadienyl) Fe-II-trifluoromethansulfonat.(Η 6 -Cumol) (η 5 cyclopentadienyl) Fe-II-trifluoromethanesulfonate is used as the photoinitiator.

Die Herstellung der Klebstofformulierungen und die Messung der Zugscherfestigkeit erfolgt wie bei Beispielen 1-27 beschrieben. Die Härtung der belichteten Proben erfolgt hier allerdings bei 140 bzw. 150°C. Die Ergebnisse findet man in der folgenden Tabelle

Figure imgb0025
The preparation of the adhesive formulations and the measurement of the tensile shear strength are carried out as described in Examples 1-27. However, the exposed samples are cured here at 140 or 150 ° C. The results can be found in the following table
Figure imgb0025

Claims (9)

1. Zusammensetzungen enthaltend A) ein Epoxidharz mit durchschnittlich mindestens zwei 1,2-Epoxidgruppen pro Molekül oder ein Gemisch dieser Epoxidharze, B) eine Verbindung der Formel I oder ein Gemisch dieser Verbindungen
Figure imgb0026
worin a und b unabhängig voneinander 1 oder 2 sind, Ri ein n-Aren ist, R2 ein n-Aren, ein Indenylanion oder ein Cyclopentadienylanion bedeutet, Xe ein Anion [LQm]° oder ein Anion einer teil-oder perfluorierten aliphatischen oder aromatischen Sulfonsäure ist, L B, P, As oder Sb bedeutet, Q Fluor ist oder ein Teil der Reste Q auch Hydroxylgruppen sein können und m der um Eins vergrösserten Wertigkeit von L entspricht, und C) einen mit durchschnittlich mindestens zwei Carboxylgruppen terminierten flexiblen Polyester, der sich ableitet von einem aliphatischen oder cycloaliphatischen Polyol oder einem Gemisch solcher Polyole und einer aliphatischen, cycloaliphatischen oder aromatischen Polycarbonsäure oder einem Gemisch solcher Polycarbonsäuren. 1. Containing compositions A) an epoxy resin with an average of at least two 1,2-epoxy groups per molecule or a mixture of these epoxy resins, B) a compound of formula I or a mixture of these compounds
Figure imgb0026
 wherein a and b are independently 1 or 2, R i is an n-arene, R 2 is an n-arene, an indenyl anion or a cyclopentadienyl anion, X e is an anion [LQ m] ° or an anion of a partially or perfluorinated is aliphatic or aromatic sulfonic acid, means LB, P, As or Sb, Q is fluorine or part of the radicals Q can also be hydroxyl groups and m corresponds to the value of L which is increased by one, and C) a flexible polyester terminated with an average of at least two carboxyl groups, which is derived from an aliphatic or cycloaliphatic polyol or a mixture of such polyols and an aliphatic, cycloaliphatic or aromatic polycarboxylic acid or a mixture of such polycarboxylic acids. 2. Zusammensetzungen gemäss Anspruch 1, worin Komponente A) ein Polyglycidylether auf der Basis von Phenolen ist.2. Compositions according to claim 1, wherein component A) is a polyglycidyl ether based on phenols. 3. Zusammensetzungen gemäss Anspruch 1, worin Komponente A) eine Kombination von flüssigen Diglycidylethern auf Bisphenol-Basis mit festen Diglycidylethern auf Bisphenol-Basis oder mit festen Polyglycidylethern auf Basis von Phenol-Formaldehyd-Novolaken oder Kresol-Formaldehyd-Novolaken ist.3. Compositions according to claim 1, wherein component A) is a combination of liquid bisphenol-based diglycidyl ethers with solid bisphenol-based diglycidyl ethers or with solid polyglycidyl ethers based on phenol-formaldehyde novolaks or cresol-formaldehyde novolaks. 4. Zusammensetzungen gemäss Anspruch 3, worin Komponente A) eine Kombination von flüssigen und festen Bisphenol-A-Diglycidylethern ist.4. Compositions according to claim 3, wherein component A) is a combination of liquid and solid bisphenol A diglycidyl ethers. 5. Zusammensetzungen gemäss Anspruch 1 enthaltend als Komponente B) Verbindungen der Formel I, worin Ri ein ein- oder zweifach alkyl-oder alkoxy-substituierter Benzol- oder Naphthalinrest ist, R2 ein Cyclopentadienylanion ist und Xe SbF bedeutet.5. Compositions according to claim 1 containing as component B) compounds of the formula I in which R i is a mono- or disubstituted alkyl or alkoxy-substituted benzene or naphthalene radical, R 2 is a cyclopentadienyl anion and X e is SbF. 6. Zusammensetzungen gemäss Anspruch 1, worin Komponente C) eine Verbindung der Formel II ist
Figure imgb0027
worin R3 ein Rest einer aliphatischen, cycloaliphatischen oder aromatischen Dicarbonsäure nach dem Entfernen der Carboxylgruppen ist, R4 ein Rest eines zweiwertigen aliphatischen oder cycloaliphatischen Alkohols nach dem Entfernen der Hydroxylgruppen ist und c eine ganze Zahl von 1 bis 50 bedeutet.6. Compositions according to claim 1, wherein component C) is a compound of formula II
Figure imgb0027
 wherein R 3 is a residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid after removal of the carboxyl groups, R 4 is a residue of a dihydric aliphatic or cycloaliphatic alcohol after removal of the hydroxyl groups and c is an integer from 1 to 50. 7. Zusammensetzungen gemäss Anspruch 6, worin zumindest ein Teil der Reste R4 zweiwertige Reste eines Polyalkylenethers sind.7. Compositions according to claim 6, wherein at least some of the radicals R 4 are divalent radicals of a polyalkylene ether. 8. Gehärtete Produkte aus den Zusammensetzungen gemäss Anspruch 1 erhältlich durch direkte Heisshärtung oder durch Härtung mittels einer kombinierten Behandlung mit aktinischer Strahlung und Wärme.8. Hardened products from the compositions according to claim 1 obtainable by direct hot curing or by curing by means of a combined treatment with actinic radiation and heat. 9. Verwendung der Zusammensetzungen gemäss Anspruch 1 als Oberflächenbeschichtungen oder als Klebstoffe.9. Use of the compositions according to claim 1 as surface coatings or as adhesives.
EP88810851A 1987-12-18 1988-12-09 Flexibilised epoxy resin compositions Expired - Lifetime EP0321407B1 (en)

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EP0511405A4 (en) * 1990-11-16 1993-04-14 Nippon Kayaku Kabushiki Kaisha Cationically polymerizable organic material composition and stabilization of said composition
US5359017A (en) * 1990-11-16 1994-10-25 Nippon Kayaku Kabushiki Kaisha Cationically polymerizable organic material compositions and method for the stabilization thereof
EP0540466A2 (en) * 1991-10-28 1993-05-05 Ciba-Geigy Ag Solvent-free curable resin compositions, especially for the production of prepregs
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EP0843685A1 (en) * 1995-07-26 1998-05-27 Lockheed Martin Energy Systems, Inc. Ionizing radiation curing of epoxy resin systems incorporating cationic photoinitiators
EP0843685A4 (en) * 1995-07-26 1998-10-28 Lockheed Martin Energy Sys Inc Ionizing radiation curing of epoxy resin systems incorporating cationic photoinitiators
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